US9424959B2 - Conductive full vulcanized thermoplastic elastomer and its preparation method - Google Patents
Conductive full vulcanized thermoplastic elastomer and its preparation method Download PDFInfo
- Publication number
- US9424959B2 US9424959B2 US14/001,948 US201214001948A US9424959B2 US 9424959 B2 US9424959 B2 US 9424959B2 US 201214001948 A US201214001948 A US 201214001948A US 9424959 B2 US9424959 B2 US 9424959B2
- Authority
- US
- United States
- Prior art keywords
- rubber
- full vulcanized
- component
- conductive
- powdered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active, expires
Links
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920001971 elastomer Polymers 0.000 claims abstract description 123
- 239000005060 rubber Substances 0.000 claims abstract description 123
- 239000002245 particle Substances 0.000 claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 48
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 48
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 31
- 239000011231 conductive filler Substances 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- -1 polypropylene Polymers 0.000 claims description 44
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 35
- 239000004698 Polyethylene Substances 0.000 claims description 31
- 229920003023 plastic Polymers 0.000 claims description 31
- 239000004033 plastic Substances 0.000 claims description 31
- 229920000573 polyethylene Polymers 0.000 claims description 31
- 239000004743 Polypropylene Substances 0.000 claims description 30
- 229920001155 polypropylene Polymers 0.000 claims description 30
- 229920000459 Nitrile rubber Polymers 0.000 claims description 24
- 229920002857 polybutadiene Polymers 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002048 multi walled nanotube Substances 0.000 claims description 7
- 229920002379 silicone rubber Polymers 0.000 claims description 7
- 239000004945 silicone rubber Substances 0.000 claims description 7
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- YFRNYWVKHCQRPE-UHFFFAOYSA-N buta-1,3-diene;prop-2-enoic acid Chemical compound C=CC=C.OC(=O)C=C YFRNYWVKHCQRPE-UHFFFAOYSA-N 0.000 claims description 4
- 229920005549 butyl rubber Polymers 0.000 claims description 4
- 229920003049 isoprene rubber Polymers 0.000 claims description 4
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 4
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
- 229920001021 polysulfide Polymers 0.000 claims description 4
- 239000005077 polysulfide Substances 0.000 claims description 4
- 150000008117 polysulfides Polymers 0.000 claims description 4
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000002079 double walled nanotube Substances 0.000 claims description 2
- 239000004700 high-density polyethylene Substances 0.000 claims description 2
- 229920004889 linear high-density polyethylene Polymers 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 208000032365 Electromagnetic interference Diseases 0.000 abstract description 2
- 230000003068 static effect Effects 0.000 abstract description 2
- 238000010057 rubber processing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 27
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 9
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 9
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 7
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 6
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 4
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000011859 microparticle Substances 0.000 description 4
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241001247482 Amsonia Species 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
- C08J2325/10—Copolymers of styrene with conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
Definitions
- the invention relates to a full vulcanized thermoplastic elastomer. More specially, the invention relates to a conductive full vulcanized thermoplastic elastomer and its preparation method.
- Full vulcanized thermoplastic elastomer is a new material developed in 1980's and it has characteristic performances of both plastics and rubber, which shows high elasticity of rubber at room temperature and can be also plasticizing-shaped at high temperature.
- the strength, elasticity, heat resistance and compressive permanent deformation resistance of full vulcanized thermoplastic elastomer are much higher than those of non-crosslinked thermoplastic elastomer, and at the same time its chemistry resistance and processing stability are significantly improved, and the blending ratio of rubber and plastics can vary in a broader range such that the material performance can adjust largely and thus its application ranges are very broad.
- full vulcanized thermoplastic elastomer is prepared by dynamic vulcanization of thermoplastic elastomer and rigid thermoplastic plastics under certain condition.
- China patent CN1184265C of the applicant provides a full vulcanized thermoplastic elastomer having controllable particle diameter of rubber phase and sphere-like shape and its preparation method.
- Such full vulcanized thermoplastic elastomer is prepared through common blending method for processing rubber and plastics by blending and granulating full vulcanized powdered rubber and plastics via rubber plastics blending equipment.
- the weight ratio of full vulcanized powdered rubber to plastics is in the range from 30:70 to 75:25, preferably 50:50-75:25, wherein rubber component is rubber particle having crosslinking structure and its mean particle diameter is in the range from 0.02 to 1 ⁇ m, preferably 0.05 to 0.5 ⁇ m, more preferably 0.05 to 0.2 ⁇ m.
- rubber particle has gel content of 60 wt % or greater which can be selected from the full vulcanized powdered rubber prepared from international patent application WO01/40356 filed on Sep.
- full vulcanized powdered rubber selected from the group consisting of full vulcanized powdered natural rubber, full vulcanized powdered styrene butadiene rubber, full vulcanized powdered carboxylic styrene butadiene rubber, full vulcanized powdered nitrile rubber, full vulcanized powdered carboxylic nitrile rubber, full vulcanized powdered polybutadiene rubber, full vulcanized powdered chloroprene rubber, full vulcanized powdered silicone rubber, full vulcanized powdered acrylate rubber, full vulcanized powdered butadiene-styrene-vinylpyridine rubber, full vulcanized powdered isoprene rubber, full vulcanized powdered butyl rubber, full vulcanized powdered polysulfide rubber, full vulcanized powdered acrylate-butadiene rubber, full vulcan
- China patent CN1381524A of the applicant provides a full vulcanized polyolefin thermoplastic elastomer and its preparation method.
- Such full vulcanized polyolefin thermoplastic elastomer is prepared by blending components including polyolefin plastics and rubber, wherein the weight ratio of rubber component to polyolefin plastics is in the range from 30:70 to 75:25, preferably 50:50 to 75:25, and rubber component is rubber particle having crosslinking structure.
- Such rubber particle is preferably homogenous phase structure and its mean particle diameter is in the range from 0.02 to 1 ⁇ m, preferably 0.05 to 0.5 ⁇ m, more preferably 0.05 to 0.3 ⁇ m.
- Such rubber particle has gel content of 60 wt % or greater, preferably 80 wt % or greater which can be selected from the full vulcanized powdered rubber prepared from international patent application WO01/40356 (priority date: Dec. 3, 1999) filed on Sep.
- vulcanized powdered rubber selected from the group consisting of full vulcanized powdered natural rubber, full vulcanized powdered styrene butadiene rubber, full vulcanized powdered polybutadiene rubber and full vulcanized powdered silicone rubber etc.
- such rubber particle can be selected from the crosslinked type powdered rubber prepared from China patent CN1353131A of the applicant (application date: Nov. 3, 2000, Patent number ZL00130386.4) which can comprise at least one of crosslinked type powdered styrene butadiene rubber and crosslinked type powdered polybutadiene rubber etc.
- the polyolefin plastics of full vulcanized polyolefin thermoplastic elastomer comprises homopolymer, copolymer of polyolefin plastics and blends thereof and preferably at least one of polypropylene, polypropylene copolymer, polyethylene and polyethylene copolymer etc.
- the above full vulcanized thermoplastic elastomer was prepared through common blending method for processing rubber and plastics by melt-blending and granulating components including full vulcanized powdered rubber and plastics via rubber plastics blending equipment under common plastics processing temperature.
- the full vulcanized thermoplastic elastomers provided by CN11842650 and CN1381524A have good controllable particle diameter and gel content of rubber phase and good mechanic properties compared to the full vulcanized thermoplastic elastomer prepared by traditional dynamic vulcanization method. In particular, they have higher whiteness value and can be easily made into light colorful products, and can be easily dyed and made into other colorful products.
- the preparation methods of full vulcanized thermoplastic elastomers from these patent applications are simple. Contrast to the dynamic vulcanization method, common rubber plastics blending equipment is used without particular equipments, and the process is simple and the processing conditions can be controlled easily, and furthermore, the controllability of rubber phase particle diameter and crosslinking degree are good.
- the full vulcanized thermoplastic elastomers prepared by CN1184265C and CN1381524A are not conductive, which are not suitable to particular applications requiring conductivity.
- thermoplastic elastomers when full vulcanized thermoplastic elastomers are prepared by blending method with thermoplastic plastics as continuous phase and rubber particle having crosslinking structure such as full vulcanized powdered rubber as dispersed phase, only small amount of carbon nanotubes need to be added to form effective conductive channel such that the resulting thermoplastic elastomers have good conductivity and their other original properties are not affected substantially, because full vulcanized powdered rubber were vulcanized before blending which is dispersed phase during blending and can be dispersed homogeneously in the plastics matrix such that the added carbon nanotubes cannot be dispersed or embedded in the rubber phase and can be dispersed in the plastics continuous phase and can be distributed between rubber dispersed phase when small amount of conductive material such as carbon nanotubes are added.
- An object of this invention is to provide conductive full vulcanized thermoplastic elastomers with good conductivity.
- Another object of this invention is to provide a method for preparing the conductive full vulcanized thermoplastic elastomers.
- the conductive full vulcanized thermoplastic elastomers are prepared by blending plastics, rubber particle and conductive fillers once, wherein the process is simple and the use amount of conductive fillers is less.
- the full vulcanized thermoplastic elastomers according to the invention comprise the following components in the form of mixture: (a) thermoplastic plastics; (b) rubber particles having crosslinking structure; (c) conductive fillers; wherein rubber particles of component (b) have mean particle diameter of 0.02 to 1 ⁇ m and gel content of 60 wt % or greater, and conductive fillers of component (c) are carbon nanotubes;
- the microscopic phase state of the conductive full vulcanized thermoplastic elastomer is that thermoplastic plastics of component (a) are continuous phase, rubber particles of component (b) are dispersed phase, and carbon nanotubes of component (c) are dispersed in the continuous phase and distributed between the rubber particles;
- the weight ratio of rubber particles of component (h) to thermoplastic plastics of component (a) is from 30:70 to 75:25, preferably 50:50 to 75:25, and the content of conductive fillers of component (c) is from 0.3 to 10 weight parts, preferably 0.5 to 10 weight parts, more preferably 0.5 to 7 weight parts, most preferably 2 to 7 weight parts based on the total weight of rubber particles of component (b) and thermoplastic plastics of component (a) of 100 weight parts.
- component (b) is rubber particle having crosslinking structure, preferably rubber particle having homogeneous phase structure, and the mean particle diameter of rubber particle is 0.02 to 1 ⁇ m, preferably 0.05 to 0.5 ⁇ m, more preferably 0.05 to 0.2 ⁇ m, and the gel content of rubber particle is 60 wt % or greater, preferably 75 wt % or greater.
- the gel content of rubber phase in the resulting conductive full vulcanized thermoplastic elastomers is the gel content of the rubber particle having crosslinking structure itself.
- rubber types as dispersed phase there is no limit for rubber types as dispersed phase, and it can be at least one rubber selected from the group consisting of natural rubber, styrene butadiene rubber, carboxylic styrene butadiene rubber, nitrile rubber, carboxylic nitrile rubber, polybutadiene rubber, silicone rubber, chloroprene rubber, acrylate rubber, butadiene-styrene-vinylpyridine rubber, isoprene rubber, butyl rubber, polysulfide rubber, acrylate-butadiene rubber, polyurethane rubber and fluorubber.
- natural rubber styrene butadiene rubber, carboxylic styrene butadiene rubber, nitrile rubber, carboxylic nitrile rubber, polybutadiene rubber, silicone rubber, chloroprene rubber, acrylate rubber, butadiene-styrene-vinylpyridine rubber, isoprene rubber, but
- the above rubber particles having crosslinking structure of component (b) are full vulcanized powdered rubber prepared according to international patent application WO01/40356 (priority date: Dec. 3, 1999) filed on Sep. 18, 2000 and international patent application WO01/98395 (priority date: Jun. 15, 2000) filed on Jun. 15, 2001 of the applicant.
- At least one of the following full vulcanized powdered rubber are preferably used during the preparation: full vulcanized powdered natural rubber, full vulcanized powdered styrene butadiene rubber, full vulcanized powdered carboxylic styrene butadiene rubber, full vulcanized powdered nitrile rubber, full vulcanized powdered carboxylic nitrile rubber, full vulcanized powdered polybutadiene rubber, full vulcanized powdered chloroprene rubber, full vulcanized powdered silicone rubber, full vulcanized powdered acrylate rubber, full vulcanized powdered butadiene-styrene-vinylpyridine rubber, full vulcanized powdered isoprene rubber, full vulcanized powdered butyl rubber, full vulcanized powdered polysulfide rubber, full vulcanized powdered acrylate-butadiene rubber, full vulcanized
- Such full vulcanized powdered rubber mean free flowing rubber micro powder having gel content of 60 wt % or greater, preferably 75 wt % or greater after drying without adding parting agent.
- the mean particle diameter of powdered rubber in these patent applications is 0.02 to 1 ⁇ m, preferably 0.05 to 0.5 ⁇ m, more preferably 0.05 to 0.2 ⁇ m.
- Each microparticle of such full vulcanized powdered rubber is homogeneous, that is, composition of single microparticle is homogeneous and there is no inhomogeneous phenomenon such as lamination and phase separation etc under modern microscope technology. Particle diameter of such powdered rubber is fixed by irradiation crosslinking corresponding rubber latex.
- the above rubber particles can be also crosslinked type powdered rubber prepared according to China patent CN1353131A of the applicant (application date: Nov. 3, 2000, Patent number ZL00130386.4) which comprise at least one crosslinked type powdered rubber of crosslinked type powdered styrene butadiene rubber and crosslinked type powdered polybutadiene rubber etc.
- Such crosslinked type powdered rubber is a powdered rubber obtained through drying with crosslinked type synthesis rubber emulsion as raw material.
- Such crosslinked type powdered rubber is free flowing without adding parting agent.
- the mean particle diameter of powdered rubber in this patent CN1353131 is 0.05 to 0.3 ⁇ m, and its gel content is 80 wt % or greater, preferably 85 wt % or greater which is consistent with the gel content of crosslinked type synthesis rubber emulsion as raw material.
- Each microparticle of such crosslinked type powdered rubber is homogeneous, that is, composition of single microparticle is homogeneous and there is no inhomogeneous phenomenon such as lamination and phase separation etc under modern microscope technology.
- thermoplastic plastics of component (a) according to the conductive full vulcanized thermoplastic elastomer can be selected from various thermoplastic plastics in the art, and preferably comprise at least one selected from the group consisting of polypropylene, polyethylene, polyamide, polyvinylchloride, polyurethane, polyester, polycarbonate, polyformaldehyde, polystyrene, polyphenylene sulfide, polyimide, and polysulfone and grafting modified substances of such thermoplastic plastics above (such as grafted polyethylene, grafted polypropylene etc).
- the above polyethylene preferably comprises at least one selected from the group consisting of low density polyethylene, linear low density polyethylene, high density polyethylene and various grafted polyethylene etc, more preferably linear low density polyethylene, grafted polyethylene or blends thereof etc.
- the above polypropylene preferably comprises at least one selected from the group consisting of polypropylene homopolymer, polypropylene copolymer and grafted polypropylene etc.
- conductive fillers of conductive full vulcanized thermoplastic elastomer can be selected from carbon nanotubes including single walled carbon nanotubes, double wall carbon nanotubes, multi-walled carbon nanotubes or mixtures thereof, preferably multi-walled carbon nanotubes.
- carbon nanotubes are generally selected from carbon nanotubes having mean diameter of 0.4 to 500 nm, mean length of 0.1 to 1000 ⁇ m and aspect of 0.25 to 2.5 ⁇ 10 6 , preferably carbon nanotubes having mean diameter of 1 to 50 nm, mean length of 1 to 50 ⁇ m and aspect of 20 to 1 ⁇ 10 4 according to current market condition and material availability.
- Some common aiding agents during the processing of full vulcanized thermoplastic plastics can be included in the conductive full vulcanized thermoplastic elastomer according to the invention, which comprise for example antioxidants, colorants, processing aiding agents etc, and their use amount are conventional amounts or can be adjusted according to practice case.
- the invention also provides a method for preparing the conductive full vulcanized thermoplastic elastomer according to the invention, wherein components including the thermoplastic plastics of component (a), the rubber particles having crosslinking structure of component (b) and the conductive fillers of component (c) according to the invention are subjected to pass through rubber plastics blending equipment and melt-blended once to obtain the conductive full vulcanized thermoplastic elastomer by common melt-blending method for processing rubber and plastics.
- the blending temperature of materials i.e. common processing temperature of the thermoplastic plastics
- the blending temperature of materials shall be selected from the range of temperatures which can guarantee the full melting of thermoplastic plastics and cannot decompose it.
- suitable amount of common aiding agents for processing plastics can be added into blending materials.
- each component of rubber particles, conductive fillers and thermoplastic plastics etc can be metered and added into melt-blending equipment simultaneously for melt-blending.
- each component are firstly premixed evenly through common mixing equipment and then once melt-blended and extruded through rubber plastics blending equipment to obtain the full vulcanized thermoplastic elastomer.
- the rubber plastics blending equipments used in the preparation according to the invention can be mixing mill, internal mixer, single screw extruder, double screw extruder or torque rheometer etc.
- the material mixing equipments are selected from mechanic mixing equipments such as high speed mixer, kneader etc in the art.
- the conductive full vulcanized thermoplastic elastomer according to the invention is obtained by once melt-blending components including rubber particles having crosslinking structure, thermoplastic plastics and conductive fillers etc. Only small amount of conductive fillers need to be added to form effective conductive channel such that the resulting thermoplastic elastomers have good conductivity and combination properties simultaneously, because rubber phase had crosslinking structure before preparation and is dispersed phase during preparation and can be dispersed homogeneously in the plastics continuous phase during blending such that the conductive fillers cannot be dispersed or embedded in the rubber phase and can be dispersed in the plastics continuous phase and can be distributed between rubber particles.
- the resulting conductive full vulcanized thermoplastic elastomers according to the invention can be used to produce electronic production equipment, means, electronic instrument, instrument housing and decorative materials of clean production workshop having static resistance, electro magnetic interference resistance and clean requirement.
- the preparation method of the invention uses common rubber plastics blending equipment, general melt-blending extrusion method, rubber particles having crosslinking structure and conductive fillers under conventional blending process conditions to prepare conductive full vulcanized thermoplastic elastomers, and thus its process is simple and the equipment is low cost, processing performance can be improved, process conditions can be easily controlled, the amount of conductive fillers of the resulting products are low and can be suitable for the requirement of batch production in the industry.
- FIG. 1 is a graph of transmission electron microscope (TEM) of microscopic phase state of the resulting full vulcanized thermoplastic elastomers according to example 1-5.
- TEM transmission electron microscope
- FIG. 2 is a graph of transmission electron microscope (TEM) of microscopic phase state of the resulting full vulcanized thermoplastic elastomers according to example 2-10.
- TEM transmission electron microscope
- FIG. 3 is a graph of transmission electron microscope (TEM) of microscopic phase state of the resulting full vulcanized thermoplastic elastomers according to example 3-1.
- TEM transmission electron microscope
- Full vulcanized powdered styrene butadiene rubber (Beijing Research Institute of Chemical Industry of China Petroleum & Chemical Corporation, VP101A, gel content of 84 wt %, mean particle diameter of 100 nm), carbon nanotubes (Beijing Cnano Technology Co., Ltd, FloTube 9000, multi-walled carbon nanotubes, mean length of 10 ⁇ m, mean diameter of 11 nm), linear low density polyethylene (Qilu company of China Petroleum & Chemical Corporation, model 7042), antioxidant 1010 (produced by Ciba-Geigy, Switzerland) and 168 (produced by Ciba-Geigy, Switzerland) are mixed sufficiently in the mixer, wherein the weight ratio of full vulcanized powdered rubber to polyethylene is 60/40, the weight ratio of carbon nanotubes to the total weight of polyethylene and full vulcanized powdered rubber is 3/100, antioxidants 1010 and 168 constitute 0.2 wt % and 0.4 wt
- the revolution of torque rheometer is 60 revolution/minute (rpm).
- the materials are discharged after plasticized evenly.
- the resulting sample are made into sheets by using double roller mill (the temperature is set to 200° C.), and the materials are made into standard strips by using molding method and various properties are measured.
- the measure results of conductive full vulcanized styrene butadiene rubber/polyethylene thermoplastic elastomer are listed in table 1.
- Example 1-2 is same as example 1-1, except that the weight ratio of carbon nanotubes to the total weight of polyethylene and full vulcanized powdered styrene butadiene rubber is 4/100.
- the measure results of conductive full vulcanized styrene butadiene rubber/polyethylene thermoplastic elastomer are listed in table 1.
- Example 1-3 is same as example 1-1, except that the weight ratio of carbon nanotubes to the total weight of polyethylene and full vulcanized powdered styrene butadiene rubber is 5/100.
- the measure results of conductive full vulcanized styrene butadiene rubber/polyethylene thermoplastic elastomer are listed in table 1.
- Example 1-4 is same as example 1-1, except that the weight ratio of carbon nanotubes to the total weight of polyethylene and full vulcanized powdered styrene butadiene rubber is 6/100.
- the measure results of conductive full vulcanized styrene butadiene rubber/polyethylene thermoplastic elastomer are listed in table 1.
- Comparative example 1-1 is same as example 1-1, except that carbon nanotubes are not added. The experiment results are listed in table 1.
- Example 1-5 is same as example 1-2, except that the weight ratio of full vulcanized powdered styrene butadiene rubber to polyethylene is 40/60.
- the measure results of conductive full vulcanized styrene butadiene rubber/polyethylene thermoplastic elastomer are listed in table 1.
- FIG. 1 shows a graph of transmission electron microscope (TEM) of microscopic phase state of the resulting full vulcanized thermoplastic elastomers according to this example, wherein the black granulate shadow is full vulcanized powdered styrene butadiene and the tube-like substances distributed between particles are carbon nanotubes.
- TEM transmission electron microscope
- Comparative example 1-2 is same as example 1-5, except that carbon nanotubes are not added. The experiment results are listed in table 1.
- Example 1-6 is same as example 1-2, except that the weight ratio of full vulcanized powdered styrene butadiene rubber to polyethylene is 50/50.
- the measure results of conductive full vulcanized styrene butadiene/polyethylene thermoplastic elastomer are listed in table 1.
- Comparative example 1-3 is same as example 1-6, except that carbon nanotubes are not added. The experiment results are listed in table 1.
- Example 1-7 is same as example 1-2, except that the weight ratio of full vulcanized powdered styrene butadiene rubber to polyethylene is 70/30.
- the measure results of conductive full vulcanized styrene butadiene/polyethylene thermoplastic elastomer are listed in table 1.
- Comparative example 1-4 is same as example 1-7, except that carbon nanotubes are not added.
- the experiment results are listed in table 1.
- Example 1-8 is same as example 1-5, except that full vulcanized powdered styrene butadiene rubber is placed by full vulcanized powdered nitrile rubber (Beijing Research Institute of Chemical Industry of China Petroleum & Chemical Corporation, VP101A, gel content of 93 wt %, mean particle diameter of 100 nm) and the weight ratio of carbon nanotubes to the total weight of polyethylene and full vulcanized powdered nitrile rubber is 3/100.
- the measure results of conductive full vulcanized nitrile rubber/polyethylene thermoplastic elastomer are listed in table 1.
- Comparative example 1-5 is same as example 1-8, except that carbon nanotubes are not added.
- the experiment results are listed in table 1,
- antioxidant 1010 produced by Ciba-Geigy, Switzerland
- 168 produced by Ciba-Geigy, Switzerland
- the weight ratio of powdered rubber to polypropylene is 70/30
- the weight ratio of carbon nanotubes to the total weight of polypropylene and powdered robber is 2/100
- antioxidants 1010 and 168 constitute 0.2 wt % and 0.4 wt % of the total weight of powdered rubber and polypropylene, respectively, and subsequently are melt-blended using Branbender torque rheometer, wherein the oil bath temperature for blending is 210° C.
- the revolution of torque rheometer is 70 revolution/minute (rpm).
- the materials are discharged after plasticized evenly.
- the resulting sample are made into sheets by using double roller mill (the temperature is set to 200° C.), and the materials are made into standard strips by using molding method and various properties are measured.
- the measure results of conductive full vulcanized carboxylic nitrile rubber/polypropylene thermoplastic elastomer are listed in table 2.
- Example 2-2 is same as example 2-1, except that the weight ratio of carbon nanotubes to the total weight of polypropylene and full vulcanized powdered carboxylic nitrile rubber is 4/100.
- the measure results of conductive full vulcanized carboxylic nitrile rubber/polypropylene thermoplastic elastomer are listed in table 2.
- Example 2-3 is same as example 2-1, except that the weight ratio of carbon nanotubes to the total weight of polypropylene and full vulcanized powdered carboxylic nitrile rubber is 7/100.
- the measure results of conductive full vulcanized carboxylic nitrile rubber/polypropylene thermoplastic elastomer are listed in table 2.
- Example 2-4 is same as example 2-1, except that the weight ratio of carbon nanotubes to the total weight of polypropylene and full vulcanized powdered carboxylic nitrile rubber is 0.5/100.
- the measure results of conductive full vulcanized carboxylic nitrile rubber/polypropylene thermoplastic elastomer are listed in table 2.
- Comparative example 2-1 is same as example 2-1, except that carbon nanotubes are not added.
- the experiment results are listed in table 2.
- Example 2-5 is same as example 2-2, except that the weight ratio of full vulcanized powdered carboxylic nitrile rubber to polypropylene is 60/40.
- the measure results of conductive full vulcanized carboxylic nitrile/polypropylene thermoplastic elastomer are listed in table 2.
- Example 2-6 is same as example 2-2, except that the weight ratio of full vulcanized powdered carboxylic nitrile rubber to polypropylene is 50/50.
- the measure results of conductive full vulcanized carboxylic nitrile/polypropylene thermoplastic elastomer are listed in table 2.
- Example 2-7 is same as example 2-2, except that the weight ratio of full vulcanized powdered carboxylic nitrile rubber to polypropylene is 75/25.
- the measure results of conductive full vulcanized carboxylic nitrile/polypropylene thermoplastic elastomer are listed in table 2.
- Example 2-8 is same as example 2-1, except that full vulcanized powdered carboxylic nitrile rubber is placed by full vulcanized powdered styrene butadiene rubber (Beijing Research Institute of Chemical Industry of China Petroleum & Chemical Corporation, VP101A, gel content of 84 wt %, mean particle diameter of 100 nm).
- the measure results of conductive full vulcanized styrene butadiene rubber/polypropylene thermoplastic elastomer are listed in table 2.
- Comparative example 2-2 is same as example 2-8, except that carbon nanotubes are not added. The experiment results are listed in table 2.
- Example 2-9 is same as example 2-1, except that full vulcanized powdered carboxylic nitrile rubber is placed by full vulcanized powdered silicone rubber (Beijing Research Institute of Chemical Industry of China Petroleum & Chemical Corporation, VP601A, gel content of 81 wt %, mean particle diameter of 150 nm).
- the measure results of conductive full vulcanized silicone rubber/polypropylene thermoplastic elastomer are listed in table 9.
- Comparative example 2-3 is same as example 2-9, except that carbon nanotubes are not added. The experiment results are listed in table 2.
- Example 2-10 is same as example 2-1, except that polypropylene is placed by maleic anhydride grafted polypropylene (Ningbo Nengzhiguang New Materials Technology Co., Ltd, GPM200AL, grafting ratio of 0.8 wt %).
- FIG. 2 shows a graph of transmission electron microscope (TEM) of microscopic phase state of the resulting full vulcanized thermoplastic elastomers according to this example.
- TEM transmission electron microscope
- Full vulcanized powdered carboxylic styrene butadiene rubber (Beijing Research Institute of Chemical Industry of China Petroleum & Chemical Corporation, VP201, gel content of 87 wt %, mean particle diameter of 150 nm), carbon nanotubes (Beijing Cnano Technology Co., Ltd, FloTube 9000, multi-walled carbon nanotubes, mean length of 10 ⁇ m, mean diameter of 11 nm), Nylon 6 (UBE, Japan, 1013B), antioxidant 1010 (produced by Ciba-Geigy, Switzerland) and 168 (produced by Ciba-Geigy, Switzerland) are mixed sufficiently in the mixer, wherein the weight ratio of full vulcanized powdered carboxylic styrene butadiene rubber to Nylon 6 is 50/50, the weight ratio of carbon nanotubes to the total weight of Nylon 6 and full vulcanized powdered carboxylic styrene butadiene rubber is 4/100, antioxidant
- TEM transmission electron microscope
- Comparative example 3-1 is same as example 3-1, except that carbon nanotubes are not added. The experiment results are listed in table 3.
Abstract
The invention provides a conductive full vulcanized thermoplastic elastomer and its preparation method, and relates to the technical field of full vulcanized thermoplastic elastomer. The full vulcanized thermoplastic elastomer is obtained by melt-blending components including rubber particles having crosslinking structure with mean particle diameter of 0.02 to 1 μm, carbon nanotubes as conductive fillers and thermoplastic plastics once, wherein the weight ratio of the rubber particles and the thermoplastic plastics is from 30:70 to 75:25 and the content of conductive fillers is from 0.3 to 10 weight parts based on the total weight of rubber particles and thermoplastic plastics of 100 weight parts. The resulting conductive full vulcanized thermoplastic elastomers have low content of conductive fillers and excellent combination performances. It can be prepared by conventional rubber processing methods and can be used to produce electronic production equipment, means, electronic instrument, instrument housing and decorative materials of clean production workshop having static resistance, electro magnetic interference resistance and clean requirement.
Description
The invention relates to a full vulcanized thermoplastic elastomer. More specially, the invention relates to a conductive full vulcanized thermoplastic elastomer and its preparation method.
Full vulcanized thermoplastic elastomer is a new material developed in 1980's and it has characteristic performances of both plastics and rubber, which shows high elasticity of rubber at room temperature and can be also plasticizing-shaped at high temperature. The strength, elasticity, heat resistance and compressive permanent deformation resistance of full vulcanized thermoplastic elastomer are much higher than those of non-crosslinked thermoplastic elastomer, and at the same time its chemistry resistance and processing stability are significantly improved, and the blending ratio of rubber and plastics can vary in a broader range such that the material performance can adjust largely and thus its application ranges are very broad. In traditional technology, full vulcanized thermoplastic elastomer is prepared by dynamic vulcanization of thermoplastic elastomer and rigid thermoplastic plastics under certain condition.
China patent CN1184265C of the applicant (application date: Jun. 15, 2001, priority date: Jun. 15, 2000, Patent number ZL01801655.3) provides a full vulcanized thermoplastic elastomer having controllable particle diameter of rubber phase and sphere-like shape and its preparation method. Such full vulcanized thermoplastic elastomer is prepared through common blending method for processing rubber and plastics by blending and granulating full vulcanized powdered rubber and plastics via rubber plastics blending equipment. The weight ratio of full vulcanized powdered rubber to plastics is in the range from 30:70 to 75:25, preferably 50:50-75:25, wherein rubber component is rubber particle having crosslinking structure and its mean particle diameter is in the range from 0.02 to 1 μm, preferably 0.05 to 0.5 μm, more preferably 0.05 to 0.2 μm. Such rubber particle has gel content of 60 wt % or greater which can be selected from the full vulcanized powdered rubber prepared from international patent application WO01/40356 filed on Sep. 18, 2000 by this applicant including at least one full vulcanized powdered rubber selected from the group consisting of full vulcanized powdered natural rubber, full vulcanized powdered styrene butadiene rubber, full vulcanized powdered carboxylic styrene butadiene rubber, full vulcanized powdered nitrile rubber, full vulcanized powdered carboxylic nitrile rubber, full vulcanized powdered polybutadiene rubber, full vulcanized powdered chloroprene rubber, full vulcanized powdered silicone rubber, full vulcanized powdered acrylate rubber, full vulcanized powdered butadiene-styrene-vinylpyridine rubber, full vulcanized powdered isoprene rubber, full vulcanized powdered butyl rubber, full vulcanized powdered polysulfide rubber, full vulcanized powdered acrylate-butadiene rubber, full vulcanized powdered polyurethane rubber and full vulcanized powdered fluorubber etc, and the plastics of the full vulcanized thermoplastic elastomer comprise at least one selected from the group consisting of polypropylene, polyethylene, polyamide polyvinylchloride, polyurethane, polyester, polycarbonate, polyformaldehyde, polystyrene, polyphenylene sulfide, polyimide, and polysulfone etc.
In addition, China patent CN1381524A of the applicant (application date: Apr. 18, 2001, Patent number ZL01110734.0) provides a full vulcanized polyolefin thermoplastic elastomer and its preparation method. Such full vulcanized polyolefin thermoplastic elastomer is prepared by blending components including polyolefin plastics and rubber, wherein the weight ratio of rubber component to polyolefin plastics is in the range from 30:70 to 75:25, preferably 50:50 to 75:25, and rubber component is rubber particle having crosslinking structure. Such rubber particle is preferably homogenous phase structure and its mean particle diameter is in the range from 0.02 to 1 μm, preferably 0.05 to 0.5 μm, more preferably 0.05 to 0.3 μm. Such rubber particle has gel content of 60 wt % or greater, preferably 80 wt % or greater which can be selected from the full vulcanized powdered rubber prepared from international patent application WO01/40356 (priority date: Dec. 3, 1999) filed on Sep. 18, 2000 by this applicant including at least one full vulcanized powdered rubber selected from the group consisting of full vulcanized powdered natural rubber, full vulcanized powdered styrene butadiene rubber, full vulcanized powdered polybutadiene rubber and full vulcanized powdered silicone rubber etc. Alternatively, such rubber particle can be selected from the crosslinked type powdered rubber prepared from China patent CN1353131A of the applicant (application date: Nov. 3, 2000, Patent number ZL00130386.4) which can comprise at least one of crosslinked type powdered styrene butadiene rubber and crosslinked type powdered polybutadiene rubber etc. The polyolefin plastics of full vulcanized polyolefin thermoplastic elastomer comprises homopolymer, copolymer of polyolefin plastics and blends thereof and preferably at least one of polypropylene, polypropylene copolymer, polyethylene and polyethylene copolymer etc.
The above full vulcanized thermoplastic elastomer was prepared through common blending method for processing rubber and plastics by melt-blending and granulating components including full vulcanized powdered rubber and plastics via rubber plastics blending equipment under common plastics processing temperature.
The full vulcanized thermoplastic elastomers provided by CN11842650 and CN1381524A have good controllable particle diameter and gel content of rubber phase and good mechanic properties compared to the full vulcanized thermoplastic elastomer prepared by traditional dynamic vulcanization method. In particular, they have higher whiteness value and can be easily made into light colorful products, and can be easily dyed and made into other colorful products. At the same time, the preparation methods of full vulcanized thermoplastic elastomers from these patent applications are simple. Contrast to the dynamic vulcanization method, common rubber plastics blending equipment is used without particular equipments, and the process is simple and the processing conditions can be controlled easily, and furthermore, the controllability of rubber phase particle diameter and crosslinking degree are good.
However, the full vulcanized thermoplastic elastomers prepared by CN1184265C and CN1381524A are not conductive, which are not suitable to particular applications requiring conductivity.
The applicant found in the research that when full vulcanized thermoplastic elastomers are prepared by blending method with thermoplastic plastics as continuous phase and rubber particle having crosslinking structure such as full vulcanized powdered rubber as dispersed phase, only small amount of carbon nanotubes need to be added to form effective conductive channel such that the resulting thermoplastic elastomers have good conductivity and their other original properties are not affected substantially, because full vulcanized powdered rubber were vulcanized before blending which is dispersed phase during blending and can be dispersed homogeneously in the plastics matrix such that the added carbon nanotubes cannot be dispersed or embedded in the rubber phase and can be dispersed in the plastics continuous phase and can be distributed between rubber dispersed phase when small amount of conductive material such as carbon nanotubes are added.
An object of this invention is to provide conductive full vulcanized thermoplastic elastomers with good conductivity.
Another object of this invention is to provide a method for preparing the conductive full vulcanized thermoplastic elastomers. According to the method of this invention, the conductive full vulcanized thermoplastic elastomers are prepared by blending plastics, rubber particle and conductive fillers once, wherein the process is simple and the use amount of conductive fillers is less.
The full vulcanized thermoplastic elastomers according to the invention comprise the following components in the form of mixture: (a) thermoplastic plastics; (b) rubber particles having crosslinking structure; (c) conductive fillers; wherein rubber particles of component (b) have mean particle diameter of 0.02 to 1 μm and gel content of 60 wt % or greater, and conductive fillers of component (c) are carbon nanotubes;
According to the invention, the microscopic phase state of the conductive full vulcanized thermoplastic elastomer is that thermoplastic plastics of component (a) are continuous phase, rubber particles of component (b) are dispersed phase, and carbon nanotubes of component (c) are dispersed in the continuous phase and distributed between the rubber particles;
By means of such microscopic phase state, only small amount of carbon nanotubes need to be added to form effective conductive channels such that the resulting full vulcanized thermoplastic elastomers have better conductivity and their other original properties are not affected substantially. In addition, there is no particular requirement for the size of carbon nanotubes.
In contrast, in the prior arts, when carbon nanotubes are used to modify plastics or thermoplastic elastomer materials prepared by polymerization, since there is no size exclusion effect resulted from vulcanized rubber particle as rubber phase, such particular microscopic phase state cannot occur such that carbon nanotubes are dispersed in various parts of plastics matrix or are dispersed in both continuous phase and dispersed phase of thermoplastic plastics when modifying thermoplastic elastomers, and thus enough conductive channels are able to form in the matrix to obtain conductivity after certain amount carbon nanotubes are added. Furthermore, due to large addition amount, other mechanic properties of the matrix are affected. More even, carbon nanotubes with particular size are needed to modify conductivity.
According to the conductive full vulcanized thermoplastic elastomers of this invention, the weight ratio of rubber particles of component (h) to thermoplastic plastics of component (a) is from 30:70 to 75:25, preferably 50:50 to 75:25, and the content of conductive fillers of component (c) is from 0.3 to 10 weight parts, preferably 0.5 to 10 weight parts, more preferably 0.5 to 7 weight parts, most preferably 2 to 7 weight parts based on the total weight of rubber particles of component (b) and thermoplastic plastics of component (a) of 100 weight parts.
According to the conductive full vulcanized thermoplastic elastomers of this invention, component (b) is rubber particle having crosslinking structure, preferably rubber particle having homogeneous phase structure, and the mean particle diameter of rubber particle is 0.02 to 1 μm, preferably 0.05 to 0.5 μm, more preferably 0.05 to 0.2 μm, and the gel content of rubber particle is 60 wt % or greater, preferably 75 wt % or greater. The gel content of rubber phase in the resulting conductive full vulcanized thermoplastic elastomers is the gel content of the rubber particle having crosslinking structure itself.
According to the conductive full vulcanized thermoplastic elastomers of this invention, there is no limit for rubber types as dispersed phase, and it can be at least one rubber selected from the group consisting of natural rubber, styrene butadiene rubber, carboxylic styrene butadiene rubber, nitrile rubber, carboxylic nitrile rubber, polybutadiene rubber, silicone rubber, chloroprene rubber, acrylate rubber, butadiene-styrene-vinylpyridine rubber, isoprene rubber, butyl rubber, polysulfide rubber, acrylate-butadiene rubber, polyurethane rubber and fluorubber.
Preferably, the above rubber particles having crosslinking structure of component (b) are full vulcanized powdered rubber prepared according to international patent application WO01/40356 (priority date: Dec. 3, 1999) filed on Sep. 18, 2000 and international patent application WO01/98395 (priority date: Jun. 15, 2000) filed on Jun. 15, 2001 of the applicant. At least one of the following full vulcanized powdered rubber are preferably used during the preparation: full vulcanized powdered natural rubber, full vulcanized powdered styrene butadiene rubber, full vulcanized powdered carboxylic styrene butadiene rubber, full vulcanized powdered nitrile rubber, full vulcanized powdered carboxylic nitrile rubber, full vulcanized powdered polybutadiene rubber, full vulcanized powdered chloroprene rubber, full vulcanized powdered silicone rubber, full vulcanized powdered acrylate rubber, full vulcanized powdered butadiene-styrene-vinylpyridine rubber, full vulcanized powdered isoprene rubber, full vulcanized powdered butyl rubber, full vulcanized powdered polysulfide rubber, full vulcanized powdered acrylate-butadiene rubber, full vulcanized powdered polyurethane rubber and full vulcanized powdered fluorubber etc. Such full vulcanized powdered rubber mean free flowing rubber micro powder having gel content of 60 wt % or greater, preferably 75 wt % or greater after drying without adding parting agent. The mean particle diameter of powdered rubber in these patent applications is 0.02 to 1 μm, preferably 0.05 to 0.5 μm, more preferably 0.05 to 0.2 μm. Each microparticle of such full vulcanized powdered rubber is homogeneous, that is, composition of single microparticle is homogeneous and there is no inhomogeneous phenomenon such as lamination and phase separation etc under modern microscope technology. Particle diameter of such powdered rubber is fixed by irradiation crosslinking corresponding rubber latex.
The above rubber particles can be also crosslinked type powdered rubber prepared according to China patent CN1353131A of the applicant (application date: Nov. 3, 2000, Patent number ZL00130386.4) which comprise at least one crosslinked type powdered rubber of crosslinked type powdered styrene butadiene rubber and crosslinked type powdered polybutadiene rubber etc. Such crosslinked type powdered rubber is a powdered rubber obtained through drying with crosslinked type synthesis rubber emulsion as raw material. Such crosslinked type powdered rubber is free flowing without adding parting agent. The mean particle diameter of powdered rubber in this patent CN1353131 is 0.05 to 0.3 μm, and its gel content is 80 wt % or greater, preferably 85 wt % or greater which is consistent with the gel content of crosslinked type synthesis rubber emulsion as raw material. Each microparticle of such crosslinked type powdered rubber is homogeneous, that is, composition of single microparticle is homogeneous and there is no inhomogeneous phenomenon such as lamination and phase separation etc under modern microscope technology.
The thermoplastic plastics of component (a) according to the conductive full vulcanized thermoplastic elastomer can be selected from various thermoplastic plastics in the art, and preferably comprise at least one selected from the group consisting of polypropylene, polyethylene, polyamide, polyvinylchloride, polyurethane, polyester, polycarbonate, polyformaldehyde, polystyrene, polyphenylene sulfide, polyimide, and polysulfone and grafting modified substances of such thermoplastic plastics above (such as grafted polyethylene, grafted polypropylene etc). The above polyethylene preferably comprises at least one selected from the group consisting of low density polyethylene, linear low density polyethylene, high density polyethylene and various grafted polyethylene etc, more preferably linear low density polyethylene, grafted polyethylene or blends thereof etc. The above polypropylene preferably comprises at least one selected from the group consisting of polypropylene homopolymer, polypropylene copolymer and grafted polypropylene etc.
As component (c) conductive fillers of conductive full vulcanized thermoplastic elastomer according to the invention, it can be selected from carbon nanotubes including single walled carbon nanotubes, double wall carbon nanotubes, multi-walled carbon nanotubes or mixtures thereof, preferably multi-walled carbon nanotubes. Although there is no particular requirement for the size of carbon nanotubes, carbon nanotubes are generally selected from carbon nanotubes having mean diameter of 0.4 to 500 nm, mean length of 0.1 to 1000 μm and aspect of 0.25 to 2.5×106, preferably carbon nanotubes having mean diameter of 1 to 50 nm, mean length of 1 to 50 μm and aspect of 20 to 1×104 according to current market condition and material availability.
Some common aiding agents during the processing of full vulcanized thermoplastic plastics can be included in the conductive full vulcanized thermoplastic elastomer according to the invention, which comprise for example antioxidants, colorants, processing aiding agents etc, and their use amount are conventional amounts or can be adjusted according to practice case.
The invention also provides a method for preparing the conductive full vulcanized thermoplastic elastomer according to the invention, wherein components including the thermoplastic plastics of component (a), the rubber particles having crosslinking structure of component (b) and the conductive fillers of component (c) according to the invention are subjected to pass through rubber plastics blending equipment and melt-blended once to obtain the conductive full vulcanized thermoplastic elastomer by common melt-blending method for processing rubber and plastics.
During preparation, the blending temperature of materials (i.e. common processing temperature of the thermoplastic plastics) shall be selected from the range of temperatures which can guarantee the full melting of thermoplastic plastics and cannot decompose it. In addition, according to processing requirement, suitable amount of common aiding agents for processing plastics can be added into blending materials. During blending, each component of rubber particles, conductive fillers and thermoplastic plastics etc can be metered and added into melt-blending equipment simultaneously for melt-blending. Alternatively, each component are firstly premixed evenly through common mixing equipment and then once melt-blended and extruded through rubber plastics blending equipment to obtain the full vulcanized thermoplastic elastomer.
The rubber plastics blending equipments used in the preparation according to the invention can be mixing mill, internal mixer, single screw extruder, double screw extruder or torque rheometer etc. The material mixing equipments are selected from mechanic mixing equipments such as high speed mixer, kneader etc in the art.
The conductive full vulcanized thermoplastic elastomer according to the invention is obtained by once melt-blending components including rubber particles having crosslinking structure, thermoplastic plastics and conductive fillers etc. Only small amount of conductive fillers need to be added to form effective conductive channel such that the resulting thermoplastic elastomers have good conductivity and combination properties simultaneously, because rubber phase had crosslinking structure before preparation and is dispersed phase during preparation and can be dispersed homogeneously in the plastics continuous phase during blending such that the conductive fillers cannot be dispersed or embedded in the rubber phase and can be dispersed in the plastics continuous phase and can be distributed between rubber particles. The resulting conductive full vulcanized thermoplastic elastomers according to the invention can be used to produce electronic production equipment, means, electronic instrument, instrument housing and decorative materials of clean production workshop having static resistance, electro magnetic interference resistance and clean requirement. The preparation method of the invention uses common rubber plastics blending equipment, general melt-blending extrusion method, rubber particles having crosslinking structure and conductive fillers under conventional blending process conditions to prepare conductive full vulcanized thermoplastic elastomers, and thus its process is simple and the equipment is low cost, processing performance can be improved, process conditions can be easily controlled, the amount of conductive fillers of the resulting products are low and can be suitable for the requirement of batch production in the industry.
The invention is further described by the following examples. However, the scopes of the invention are not limited by these examples, and the scopes of the invention depend on the enclosed claims.
Full vulcanized powdered styrene butadiene rubber (Beijing Research Institute of Chemical Industry of China Petroleum & Chemical Corporation, VP101A, gel content of 84 wt %, mean particle diameter of 100 nm), carbon nanotubes (Beijing Cnano Technology Co., Ltd, FloTube 9000, multi-walled carbon nanotubes, mean length of 10 μm, mean diameter of 11 nm), linear low density polyethylene (Qilu company of China Petroleum & Chemical Corporation, model 7042), antioxidant 1010 (produced by Ciba-Geigy, Switzerland) and 168 (produced by Ciba-Geigy, Switzerland) are mixed sufficiently in the mixer, wherein the weight ratio of full vulcanized powdered rubber to polyethylene is 60/40, the weight ratio of carbon nanotubes to the total weight of polyethylene and full vulcanized powdered rubber is 3/100, antioxidants 1010 and 168 constitute 0.2 wt % and 0.4 wt % of the total weight of full vulcanized powdered rubber and polyethylene, respectively, and subsequently are melt-blended using Branbender torque rheometer, wherein the oil bath temperature for blending is 200° C. and the revolution of torque rheometer is 60 revolution/minute (rpm). The materials are discharged after plasticized evenly. The resulting sample are made into sheets by using double roller mill (the temperature is set to 200° C.), and the materials are made into standard strips by using molding method and various properties are measured. The measure results of conductive full vulcanized styrene butadiene rubber/polyethylene thermoplastic elastomer are listed in table 1.
Example 1-2 is same as example 1-1, except that the weight ratio of carbon nanotubes to the total weight of polyethylene and full vulcanized powdered styrene butadiene rubber is 4/100. The measure results of conductive full vulcanized styrene butadiene rubber/polyethylene thermoplastic elastomer are listed in table 1.
Example 1-3 is same as example 1-1, except that the weight ratio of carbon nanotubes to the total weight of polyethylene and full vulcanized powdered styrene butadiene rubber is 5/100. The measure results of conductive full vulcanized styrene butadiene rubber/polyethylene thermoplastic elastomer are listed in table 1.
Example 1-4 is same as example 1-1, except that the weight ratio of carbon nanotubes to the total weight of polyethylene and full vulcanized powdered styrene butadiene rubber is 6/100. The measure results of conductive full vulcanized styrene butadiene rubber/polyethylene thermoplastic elastomer are listed in table 1.
Comparative example 1-1 is same as example 1-1, except that carbon nanotubes are not added. The experiment results are listed in table 1.
Example 1-5 is same as example 1-2, except that the weight ratio of full vulcanized powdered styrene butadiene rubber to polyethylene is 40/60. The measure results of conductive full vulcanized styrene butadiene rubber/polyethylene thermoplastic elastomer are listed in table 1. FIG. 1 shows a graph of transmission electron microscope (TEM) of microscopic phase state of the resulting full vulcanized thermoplastic elastomers according to this example, wherein the black granulate shadow is full vulcanized powdered styrene butadiene and the tube-like substances distributed between particles are carbon nanotubes.
Comparative example 1-2 is same as example 1-5, except that carbon nanotubes are not added. The experiment results are listed in table 1.
Example 1-6 is same as example 1-2, except that the weight ratio of full vulcanized powdered styrene butadiene rubber to polyethylene is 50/50. The measure results of conductive full vulcanized styrene butadiene/polyethylene thermoplastic elastomer are listed in table 1.
Comparative example 1-3 is same as example 1-6, except that carbon nanotubes are not added. The experiment results are listed in table 1.
Example 1-7 is same as example 1-2, except that the weight ratio of full vulcanized powdered styrene butadiene rubber to polyethylene is 70/30. The measure results of conductive full vulcanized styrene butadiene/polyethylene thermoplastic elastomer are listed in table 1.
Comparative example 1-4 is same as example 1-7, except that carbon nanotubes are not added. The experiment results are listed in table 1.
Example 1-8 is same as example 1-5, except that full vulcanized powdered styrene butadiene rubber is placed by full vulcanized powdered nitrile rubber (Beijing Research Institute of Chemical Industry of China Petroleum & Chemical Corporation, VP101A, gel content of 93 wt %, mean particle diameter of 100 nm) and the weight ratio of carbon nanotubes to the total weight of polyethylene and full vulcanized powdered nitrile rubber is 3/100. The measure results of conductive full vulcanized nitrile rubber/polyethylene thermoplastic elastomer are listed in table 1.
Comparative example 1-5 is same as example 1-8, except that carbon nanotubes are not added. The experiment results are listed in table 1,
| TABLE 1 | ||||||||
| Tensile | 100% | Tensile | Tensile | Compressive | ||||
| break | stretching | elongation | Permanent | Permanent | Shore | volume | ||
| strength | strength | at break | deformation | deformation | hardness | resistance | ||
| Unit |
| MPa | MPa | % | % | % | HD | Ω · CM | ||
| Example 1-1 | 10.2 | 6.5 | 330 | 24 | 26.2 | 34 | 2.4 × 108 |
| Example 1-2 | 11.1 | 7.3 | 324 | 25 | 27.6 | 35 | 6.8 × 106 |
| Example 1-3 | 11.1 | 7.4 | 300 | 27 | 27.8 | 36 | 8.1 × 104 |
| Example 1-4 | 11.4 | 7.7 | 288 | 24 | 27.1 | 36 | 6.8 × 104 |
| Comparative | 8.8 | 5.5 | 336 | 25 | 22.7 | 32 | 2.8 × 1016 |
| example1-1 | |||||||
| Example 1-5 | 12.2 | 8.4 | 436 | 60 | 34.1 | 42 | 8.8 × 107 |
| Comparative | 10.4 | 6.9 | 476 | 60 | 27.7 | 40 | 2.8 × 1016 |
| example 1-2 | |||||||
| Example 1-6 | 11.4 | 7.6 | 376 | 44 | 31.4 | 39 | 7.1 × 107 |
| Comparative | 9.0 | 5.9 | 400 | 42 | 24.0 | 36 | 2.8 × 1016 |
| example 1-3 | |||||||
| Example 1-7 | 9.9 | 6.1 | 320 | 20 | 25.6 | 32 | 3.2 × 105 |
| Comparative | 8.7 | 4.7 | 344 | 22 | 20.2 | 28 | 2.8 × 1016 |
| example 1-4 | |||||||
| Example 1-8 | — | — | — | — | 31.0 | — | 5.77 × 105 |
| Comparative | — | — | — | — | 30.0 | — | 1.8 × 1016 |
| example 1-5 | |||||||
| Measure | ASTM | ASTM | ASTM | ASTM | D395-98 | ASTM | ASTM |
| standards | D412 | D412 | D412 | D412 | D2240-95 | D257 | |
Full vulcanized powdered carboxylic nitrile rubber (Beijing Research Institute of Chemical Industry of China Petroleum & Chemical Corporation, VP501, gel content of 91 wt %, mean particle diameter of 90 nm), carbon nanotubes (Beijing Cnano Technology Co., Ltd, FloTube 9000, multi-walled carbon nanotubes, mean length of 10 μm, mean diameter of 11 nm), polypropylene (BLUESTAR Tianjin Chemical Co. Ltd, number Zero special material, homopolypropylene), antioxidant 1010 (produced by Ciba-Geigy, Switzerland) and 168 (produced by Ciba-Geigy, Switzerland) are mixed sufficiently in the mixer, wherein the weight ratio of powdered rubber to polypropylene is 70/30, the weight ratio of carbon nanotubes to the total weight of polypropylene and powdered robber is 2/100, antioxidants 1010 and 168 constitute 0.2 wt % and 0.4 wt % of the total weight of powdered rubber and polypropylene, respectively, and subsequently are melt-blended using Branbender torque rheometer, wherein the oil bath temperature for blending is 210° C. and the revolution of torque rheometer is 70 revolution/minute (rpm). The materials are discharged after plasticized evenly. The resulting sample are made into sheets by using double roller mill (the temperature is set to 200° C.), and the materials are made into standard strips by using molding method and various properties are measured. The measure results of conductive full vulcanized carboxylic nitrile rubber/polypropylene thermoplastic elastomer are listed in table 2.
Example 2-2 is same as example 2-1, except that the weight ratio of carbon nanotubes to the total weight of polypropylene and full vulcanized powdered carboxylic nitrile rubber is 4/100. The measure results of conductive full vulcanized carboxylic nitrile rubber/polypropylene thermoplastic elastomer are listed in table 2.
Example 2-3 is same as example 2-1, except that the weight ratio of carbon nanotubes to the total weight of polypropylene and full vulcanized powdered carboxylic nitrile rubber is 7/100. The measure results of conductive full vulcanized carboxylic nitrile rubber/polypropylene thermoplastic elastomer are listed in table 2.
Example 2-4 is same as example 2-1, except that the weight ratio of carbon nanotubes to the total weight of polypropylene and full vulcanized powdered carboxylic nitrile rubber is 0.5/100. The measure results of conductive full vulcanized carboxylic nitrile rubber/polypropylene thermoplastic elastomer are listed in table 2.
Comparative example 2-1 is same as example 2-1, except that carbon nanotubes are not added. The experiment results are listed in table 2.
Example 2-5 is same as example 2-2, except that the weight ratio of full vulcanized powdered carboxylic nitrile rubber to polypropylene is 60/40. The measure results of conductive full vulcanized carboxylic nitrile/polypropylene thermoplastic elastomer are listed in table 2.
Example 2-6 is same as example 2-2, except that the weight ratio of full vulcanized powdered carboxylic nitrile rubber to polypropylene is 50/50. The measure results of conductive full vulcanized carboxylic nitrile/polypropylene thermoplastic elastomer are listed in table 2.
Example 2-7 is same as example 2-2, except that the weight ratio of full vulcanized powdered carboxylic nitrile rubber to polypropylene is 75/25. The measure results of conductive full vulcanized carboxylic nitrile/polypropylene thermoplastic elastomer are listed in table 2.
Example 2-8 is same as example 2-1, except that full vulcanized powdered carboxylic nitrile rubber is placed by full vulcanized powdered styrene butadiene rubber (Beijing Research Institute of Chemical Industry of China Petroleum & Chemical Corporation, VP101A, gel content of 84 wt %, mean particle diameter of 100 nm). The measure results of conductive full vulcanized styrene butadiene rubber/polypropylene thermoplastic elastomer are listed in table 2.
Comparative example 2-2 is same as example 2-8, except that carbon nanotubes are not added. The experiment results are listed in table 2.
Example 2-9 is same as example 2-1, except that full vulcanized powdered carboxylic nitrile rubber is placed by full vulcanized powdered silicone rubber (Beijing Research Institute of Chemical Industry of China Petroleum & Chemical Corporation, VP601A, gel content of 81 wt %, mean particle diameter of 150 nm). The measure results of conductive full vulcanized silicone rubber/polypropylene thermoplastic elastomer are listed in table 9.
Comparative example 2-3 is same as example 2-9, except that carbon nanotubes are not added. The experiment results are listed in table 2.
Example 2-10 is same as example 2-1, except that polypropylene is placed by maleic anhydride grafted polypropylene (Ningbo Nengzhiguang New Materials Technology Co., Ltd, GPM200AL, grafting ratio of 0.8 wt %).
| TABLE 2 | ||||||
| Tensile | Compres- | |||||
| Perma- | sive | Shore | ||||
| Tensile | nent | Permanent | hard- | |||
| break | defor- | defor- | volume | ness | ||
| strength | mation | mation | resistance | (D) | ||
| Unit | MPa | % | % | Ω · CM | — |
| Example 2-1 | 6.4 | 8 | 42 | 7.0 × 105 | 43 |
| Example 2-2 | 7.9 | 8 | 49 | 9.3 × 104 | 51 |
| Example 2-3 | 8.5 | 4 | 47 | 4.9 × 104 | 49 |
| Example 2-4 | 5.2 | 4 | 45 | 4.7 × 1011 | 45 |
| Comparative | 7.0 | 28 | 45 | 8.7 × 1018 | 46 |
| example 2-1 | |||||
| Example 2-5 | 7.8 | 4 | 54 | 9.6 × 104 | 58 |
| Example 2-6 | 11.3 | 4 | 55 | 6.7 × 108 | 58 |
| Example 2-7 | 6.1 | 4 | 38 | 7.6 × 106 | 42 |
| Example 2-8 | 5.9 | 8 | 50 | 1.5 × 105 | 38 |
| Comparative | 6.3 | 28 | 65 | 1.7 × 1013 | 37 |
| example 2-2 | |||||
| Example 2-9 | 5.8 | 4 | 48 | 5.3 × 106 | 38 |
| Comparative | 6.8 | 28 | 46 | 3.4 × 1014 | 37 |
| example 2-3 | |||||
| Example 2-10 | 9.5 | 28 | 50 | 8.2 × 107 | 40 |
| Measure | ASTM | ASTM | ASTM | ASTM | ASTM |
| standards | D412 | D412 | D395-98 | D257 | D2240-95 |
Full vulcanized powdered carboxylic styrene butadiene rubber (Beijing Research Institute of Chemical Industry of China Petroleum & Chemical Corporation, VP201, gel content of 87 wt %, mean particle diameter of 150 nm), carbon nanotubes (Beijing Cnano Technology Co., Ltd, FloTube 9000, multi-walled carbon nanotubes, mean length of 10 μm, mean diameter of 11 nm), Nylon 6 (UBE, Japan, 1013B), antioxidant 1010 (produced by Ciba-Geigy, Switzerland) and 168 (produced by Ciba-Geigy, Switzerland) are mixed sufficiently in the mixer, wherein the weight ratio of full vulcanized powdered carboxylic styrene butadiene rubber to Nylon 6 is 50/50, the weight ratio of carbon nanotubes to the total weight of Nylon 6 and full vulcanized powdered carboxylic styrene butadiene rubber is 4/100, antioxidants 1010 and 168 constitute 0.2 wt % and 0.4 wt % of the total weight of powdered rubber and polyethylene, respectively, and subsequently are melt-blended using Branbender torque rheometer, wherein the oil bath temperature for blending is 240° C. and the revolution of torque rheometer is 60 revolution/minute (rpm). The materials are discharged after plasticized evenly. The resulting sample are made into sheets by using double roller mill (the temperature is set to 240° C.), and the materials are made into standard strips by using molding method and various properties are measured. The measure results of conductive full vulcanized powdered carboxylic styrene butadiene rubber/Nylon 6 thermoplastic elastomer are listed in table 3. FIG. 3 shows a graph of transmission electron microscope (TEM) of microscopic phase state of the resulting full vulcanized thermoplastic elastomers according to this example, wherein the black granulate shadow is full vulcanized powdered carboxylic styrene butadiene rubber and the tube-like substances distributed between particles are carbon nanotubes.
Comparative example 3-1 is same as example 3-1, except that carbon nanotubes are not added. The experiment results are listed in table 3.
| TABLE 3 | ||||||
| Tensile | Compres- | |||||
| Perma- | sive | Shore | ||||
| Tensile | nent | Permanent | hard- | |||
| break | defor- | defor- | volume | ness | ||
| strength | mation | mation | resistance | (D) | ||
| Unit | MPa | % | % | Ω · CM | — |
| Example 3-1 | — | — | 53 | 5 × 105 | — |
| Comparative | — | — | 48 | 1.0 × 1015 | — |
| example 3-1 | |||||
| Measure | ASTM | ASTM | ASTM | ASTM | ASTM |
| standards | D412 | D412 | D395-98 | D257 | D2240-95 |
Claims (17)
1. A conductive full vulcanized thermoplastic elastomer comprising the following components in the form of mixture:
(a) thermoplastic plastics; (b) rubber particles having crosslinking structure; (c) conductive fillers;
wherein the rubber particles of component (b) have mean particle diameter of 0.02 to 1 μm, gel content of 60 wt % or greater, and homogenous structure; and the conductive fillers of component (c) include carbon nanotubes;
the microscopic phase state of the conductive full vulcanized thermoplastic elastomer is that the thermoplastic plastics of component (a) are continuous phase, the rubber particles of component (b) are dispersed phase, and the carbon nanotubes of component (c) are dispersed in the continuous phase and distributed between the rubber particles and are not dispersed or embedded in the rubber phase;
wherein the weight ratio of the rubber particles of component (b) to the thermoplastic plastics of component (a) is from 30:70 to 75:25, and the content of the conductive fillers of component (c) is from 0.3 to 10 weight percentage of the total weight of the rubber particles of component (b) and the thermoplastic plastics of component (a).
2. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the thermoplastic plastics of component (a) are at least one selected from the group consisting of polypropylene, polyethylene, polyamide, polyvinylchloride, polyurethane, polyester, polycarbonate, polyformaldehyde, polystyrene, polyphenylene sulfide, polyimide, polysulfone or grafting modified substances of such thermoplastic plastics above.
3. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the rubber particles having crosslinking structure of component (b) have gel content of 75 wt % or greater.
4. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the rubber particles having crosslinking structure of component (b) have mean particle diameter of 0.05 to 0.5 μm.
5. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the carbon nanotubes are at least one selected from the group consisting of single walled carbon nanotubes, double wall carbon nanotubes and multi-walled carbon nanotubes.
6. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the carbon nanotubes are multi-walled carbon nanotubes.
7. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the carbon nanotubes have mean diameter of 0.4 to 500 nm, mean length of 0.1 to 1000 μm, and aspect ratio of 0.25 to 2.5×106.
8. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the carbon nanotubes have mean diameter of 1 to 50 nm, mean length of 1 to 50 μm, and aspect ratio of 20 to 1×104.
9. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the weight ratio of rubber particles of component (b) to thermoplastic plastics of component (a) is from 50:50 to 75:25.
10. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the content of conductive fillers of component (c) is from 0.5 to 10 weight parts based on the total weight of rubber particles of component (b) and thermoplastic plastics of component (a) of 100 weight parts.
11. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the content of conductive fillers of component (c) is from 0.5 to 7 weight parts based on the total weight of rubber particles of component (b) and thermoplastic plastics of component (a) of 100 weight parts.
12. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the thermoplastic plastics of component (a) comprises polyethylene, and wherein the polyethylene comprises at least one selected from the group consisting of low density polyethylene, linear low density polyethylene, high density polyethylene and grafted polyethylene.
13. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the thermoplastic plastics of component (a) comprises polypropylene, and wherein the polypropylene comprises at least one selected from the group consisting of polypropylene homopolymer, polypropylene copolymer and grafted polypropylene.
14. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the rubber particles having crosslinking structure of component (b) are full vulcanized powdered rubber or crosslinked type powdered rubber.
15. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the rubber particles having crosslinking structure of component (b) are full vulcanized powdered rubber comprising at least one selected from the group consisting of full vulcanized powdered natural rubber, full vulcanized powdered styrene butadiene rubber, full vulcanized powdered carboxylic styrene butadiene rubber, full vulcanized powdered nitrile rubber, full vulcanized powdered carboxylic nitrile rubber, full vulcanized powdered polybutadiene rubber, full vulcanized powdered chloroprene rubber, full vulcanized powdered silicone rubber, full vulcanized powdered acrylate rubber, full vulcanized powdered butadiene-styrene-vinylpyridine rubber, full vulcanized powdered isoprene rubber, full vulcanized powdered butyl rubber, full vulcanized powdered polysulfide rubber, full vulcanized powdered acrylate-butadiene rubber, full vulcanized powdered polyurethane rubber and full vulcanized powdered fluorubber.
16. The conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein the rubber particles having crosslinking structure of component (b) are crosslinked type powdered rubber which comprise crosslinked type powdered styrene butadiene rubber or crosslinked type powdered polybutadiene rubber.
17. A method for preparing the conductive full vulcanized thermoplastic elastomer according to claim 1 , wherein components including the thermoplastic plastics of component (a), the rubber particles having crosslinking structure of component (b) and the conductive fillers of component (c) are subjected to pass through plastics blending equipment and melt-blended once to obtain the conductive full vulcanized thermoplastic elastomer.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110052106.2 | 2011-03-04 | ||
| CN201110052093 | 2011-03-04 | ||
| CN201110052106.2A CN102653609B (en) | 2011-03-04 | 2011-03-04 | Conductive fully-vulcanized polyethylene thermoplastic elastomer and preparation method thereof |
| CN201110052106 | 2011-03-04 | ||
| CN201110052076.5A CN102653612B (en) | 2011-03-04 | 2011-03-04 | Conductive fully vulcanized polypropylene thermoplastic elastomer and preparation method thereof |
| CN201110052076 | 2011-03-04 | ||
| CN201110052093.9 | 2011-03-04 | ||
| CN201110052076.5 | 2011-03-04 | ||
| CN201110052093.9A CN102653613B (en) | 2011-03-04 | 2011-03-04 | Conductive fully-vulcanized thermoplastic elastomer and preparation method thereof |
| PCT/CN2012/071865 WO2012119526A1 (en) | 2011-03-04 | 2012-03-02 | Electrically conductive, fully vulcanized, thermoplastic elastomer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20140054512A1 US20140054512A1 (en) | 2014-02-27 |
| US9424959B2 true US9424959B2 (en) | 2016-08-23 |
Family
ID=46797485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US14/001,948 Active 2032-04-28 US9424959B2 (en) | 2011-03-04 | 2012-03-02 | Conductive full vulcanized thermoplastic elastomer and its preparation method |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US9424959B2 (en) |
| EP (1) | EP2682431B1 (en) |
| JP (1) | JP5771290B2 (en) |
| KR (1) | KR20140050576A (en) |
| ES (1) | ES2899158T3 (en) |
| WO (1) | WO2012119526A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232610B (en) * | 2013-05-14 | 2015-01-21 | 哈尔滨工业大学 | Method for preparing directionally-arranged self-assembled carbon nanotube/thermoplastic resin film |
| AU2015101952A4 (en) * | 2014-02-27 | 2019-05-16 | Vainer, Michael MR | Flexible composite material and method of producing same |
| DE102016103823A1 (en) * | 2016-03-03 | 2017-09-07 | Kraiburg Tpe Gmbh & Co. Kg | A thermoplastic elastomer composition comprising an elastomer and a non-elastomeric polyolefin functionalized with an organic carboxylic acid anhydride |
| CN107195834A (en) * | 2017-07-25 | 2017-09-22 | 江苏万达新能源科技股份有限公司 | A kind of safe electrokinetic cell aluminum hull with shock-absorbing function |
| KR102034670B1 (en) * | 2017-11-21 | 2019-11-08 | 금호석유화학 주식회사 | Electrically conductive resin composition and method of preparing the same |
| CN108912515A (en) * | 2018-07-27 | 2018-11-30 | 蒋博 | A kind of ageing-resistant ship rubber fender and preparation method thereof |
| CN111423638A (en) * | 2020-04-02 | 2020-07-17 | 浙江翔宇密封件有限公司 | High-strength rubber composite material for high-speed rail sealing element and preparation method thereof |
| CN114426716B (en) * | 2020-10-12 | 2023-05-30 | 中国石油化工股份有限公司 | Composition for preparing composite hydrogenated nitrile rubber, application of composition and composite hydrogenated nitrile rubber and preparation method of composite hydrogenated nitrile rubber |
| CN115232414B (en) * | 2021-04-23 | 2023-10-20 | 中国石油化工股份有限公司 | PVC/SBR thermoplastic vulcanized rubber composition and preparation method thereof |
| CN113502008B (en) * | 2021-07-27 | 2022-05-17 | 广西大学 | Temperature sensing rubber material and preparation method thereof |
| WO2023200944A1 (en) * | 2022-04-13 | 2023-10-19 | Meta Platforms Technologies, Llc | High aspect-ratio filler-containing conductive elastomeric materials and methods of use |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001040356A1 (en) | 1999-12-03 | 2001-06-07 | China Petro-Chemical Corporation | Full vulcanized powdered rubber with controllable particle diameter, preparing method and uses thereof |
| WO2001098395A1 (en) | 2000-06-15 | 2001-12-27 | China Petroleum & Chemical Corporation | Silicone rubber in the form of a finely divided powder, method for the production and the use of the same |
| CN1353131A (en) | 2000-11-03 | 2002-06-12 | 中国石油化工股份有限公司 | Cross-linked powdered rubber and its preparing process and usage |
| CN1381524A (en) | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Thermoplastic full-sulfurized polyolefin elastomer and its preparing process |
| US20030045638A1 (en) * | 2000-06-15 | 2003-03-06 | Jinliang Qiao | Fully cured thermoplastic elastomer, process for its manufacture and applications thereof |
| US20040144963A1 (en) | 2002-12-19 | 2004-07-29 | Thomas Braig | Conductive thermoplastics with carbon black and carbon nanofibrils |
| US20040181005A1 (en) | 2003-03-12 | 2004-09-16 | Holger Warth | Impact modified polymer compositions |
| CN1769333A (en) | 2004-10-27 | 2006-05-10 | 中国石油化工股份有限公司 | Modified wholly-vulcanised polyolefinic thermoplastic elastomer and its preparation method |
| US20070135571A1 (en) * | 2005-12-09 | 2007-06-14 | Ellul Maria D | Method for preparing thermoplastic vulcanizates with improved extrusion surfaces |
| WO2008078849A1 (en) | 2006-12-22 | 2008-07-03 | Cheil Industries Inc. | Electroconductive thermoplastic resin composition and plastic article |
| WO2009020261A1 (en) | 2007-08-08 | 2009-02-12 | Cheil Industries Inc. | Electro-conductive thermoplastic resin compositions and articles manufactured therefrom |
| EP2177570A1 (en) | 2007-07-06 | 2010-04-21 | National Institute Of Advanced Industrial Science | Structural body comprising filler and incompatible resin or elastomer, and production process or use thereof |
| CN101831090A (en) | 2010-04-02 | 2010-09-15 | 南京理工大学 | High-performance natural rubber vulcanized rubber of carbon-containing nano-tube, and preparation method thereof |
| US20100301282A1 (en) | 2007-12-27 | 2010-12-02 | Akira Minagoshi | Conductive elastomer material, and conductive sheet and conductive seamless belt each made of the material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101114992B1 (en) * | 2009-07-31 | 2012-03-06 | 주식회사 디와이엠 | Composition for Preparing Development Roller, Development Roller Using the Same, and Method for Preparing Thereof |
-
2012
- 2012-03-02 US US14/001,948 patent/US9424959B2/en active Active
- 2012-03-02 KR KR1020137021006A patent/KR20140050576A/en not_active Application Discontinuation
- 2012-03-02 WO PCT/CN2012/071865 patent/WO2012119526A1/en active Application Filing
- 2012-03-02 ES ES12755604T patent/ES2899158T3/en active Active
- 2012-03-02 JP JP2013555739A patent/JP5771290B2/en active Active
- 2012-03-02 EP EP12755604.1A patent/EP2682431B1/en active Active
Patent Citations (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6423760B1 (en) | 1999-12-03 | 2002-07-23 | China Petro-Chemical Corporation | Fully vulcanized powdery rubber having a controllable particle size, preparation and use thereof |
| WO2001040356A1 (en) | 1999-12-03 | 2001-06-07 | China Petro-Chemical Corporation | Full vulcanized powdered rubber with controllable particle diameter, preparing method and uses thereof |
| KR100851786B1 (en) | 2000-06-15 | 2008-08-13 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Fully vulcanized thermoplastic elastomer, preparation and use thereof |
| WO2001098395A1 (en) | 2000-06-15 | 2001-12-27 | China Petroleum & Chemical Corporation | Silicone rubber in the form of a finely divided powder, method for the production and the use of the same |
| US20030045638A1 (en) * | 2000-06-15 | 2003-03-06 | Jinliang Qiao | Fully cured thermoplastic elastomer, process for its manufacture and applications thereof |
| US6838490B2 (en) | 2000-06-15 | 2005-01-04 | China Petroleum & Chemical Corporation | Silicone rubber in the form of a finely divided powder, method for the production and the use of the same |
| CN1184265C (en) | 2000-06-15 | 2005-01-12 | 中国石油化工股份有限公司 | Fully cured thermoplastic elastomer, process for its manufacture and applications |
| US7491757B2 (en) | 2000-06-15 | 2009-02-17 | China Petroleum & Chemical Corporation | Fully cured thermoplastic elastomer, process for its manufacture and applications thereof |
| CN1353131A (en) | 2000-11-03 | 2002-06-12 | 中国石油化工股份有限公司 | Cross-linked powdered rubber and its preparing process and usage |
| CN1381524A (en) | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Thermoplastic full-sulfurized polyolefin elastomer and its preparing process |
| US20040144963A1 (en) | 2002-12-19 | 2004-07-29 | Thomas Braig | Conductive thermoplastics with carbon black and carbon nanofibrils |
| JP2006510763A (en) | 2002-12-19 | 2006-03-30 | ランクセス ドイチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Conductive thermoplastic resin containing carbon black and carbon nanofibers |
| KR20060052657A (en) | 2002-12-19 | 2006-05-19 | 란세스 도이치란트 게엠베하 | Conductive thermoplastics containing carbon black and carbon nanofibres |
| US20040181005A1 (en) | 2003-03-12 | 2004-09-16 | Holger Warth | Impact modified polymer compositions |
| CN1769333A (en) | 2004-10-27 | 2006-05-10 | 中国石油化工股份有限公司 | Modified wholly-vulcanised polyolefinic thermoplastic elastomer and its preparation method |
| US20070135571A1 (en) * | 2005-12-09 | 2007-06-14 | Ellul Maria D | Method for preparing thermoplastic vulcanizates with improved extrusion surfaces |
| WO2008078849A1 (en) | 2006-12-22 | 2008-07-03 | Cheil Industries Inc. | Electroconductive thermoplastic resin composition and plastic article |
| EP2177570A1 (en) | 2007-07-06 | 2010-04-21 | National Institute Of Advanced Industrial Science | Structural body comprising filler and incompatible resin or elastomer, and production process or use thereof |
| WO2009020261A1 (en) | 2007-08-08 | 2009-02-12 | Cheil Industries Inc. | Electro-conductive thermoplastic resin compositions and articles manufactured therefrom |
| CN101778894A (en) * | 2007-08-08 | 2010-07-14 | 第一毛织株式会社 | electro-conductive thermoplastic resin compositions and articles manufactured therefrom |
| US20110204298A1 (en) | 2007-08-08 | 2011-08-25 | Cheil Industries Inc. | Electro-Conductive Thermoplastic Resin Compositions and Articles Manufactured Therefrom |
| US20100301282A1 (en) | 2007-12-27 | 2010-12-02 | Akira Minagoshi | Conductive elastomer material, and conductive sheet and conductive seamless belt each made of the material |
| CN101831090A (en) | 2010-04-02 | 2010-09-15 | 南京理工大学 | High-performance natural rubber vulcanized rubber of carbon-containing nano-tube, and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| International Search Report for PCT/CN2012/071865 issued from the State Intellectual Property Office, the P.R. China, dated Jun. 14, 2012 (6 pages). |
| Supplementary European Search Report issued from European Patent Office in the corresponding European Patent Application No. 12755604, dated Apr. 2, 2015 (7 pages). |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140050576A (en) | 2014-04-29 |
| ES2899158T3 (en) | 2022-03-10 |
| EP2682431A4 (en) | 2015-05-06 |
| JP2014506948A (en) | 2014-03-20 |
| EP2682431B1 (en) | 2021-10-27 |
| EP2682431A1 (en) | 2014-01-08 |
| WO2012119526A1 (en) | 2012-09-13 |
| US20140054512A1 (en) | 2014-02-27 |
| JP5771290B2 (en) | 2015-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9424959B2 (en) | Conductive full vulcanized thermoplastic elastomer and its preparation method | |
| Huang et al. | A novel strategy to construct co-continuous PLA/NBR thermoplastic vulcanizates: Metal-ligand coordination-induced dynamic vulcanization, balanced stiffness-toughness and shape memory effect | |
| JP5420134B2 (en) | Fully vulcanized thermoplastic elastomer, its manufacture and use | |
| CN107459793B (en) | Ultra-tough polylactic acid based nano composite material of strong and unyielding equilibrium and preparation method thereof | |
| Zheng et al. | Localization control of carbon nanotubes in immiscible polymer blends through dynamic vulcanization | |
| Zhang et al. | Compatibility of waste rubber powder/polystyrene blends by the addition of styrene grafted styrene butadiene rubber copolymer: effect on morphology and properties | |
| HUE030291T2 (en) | Masterbatches for preparing a composite materials with enhanced conductivity properties, process and composite materials produced | |
| CN104497468A (en) | High-strength heat-resistant styrene thermoplastic elastomer and preparation method thereof | |
| CN109354773A (en) | The nucleating agent application tackiness in the precipitation for reducing PP composite material | |
| JP7027072B2 (en) | Each manufacturing method of thermoplastic resin composition and fiber material and film material using it | |
| EP3268425B1 (en) | A polymer nanocomposite, process and applications thereof | |
| CN106700253B (en) | A kind of low-contraction low-density PP material and preparation method thereof | |
| CN102888102A (en) | Nylon 11/polyvinylidene fluoride composition and preparation method thereof | |
| CN109810421A (en) | Semi-transparent display HIPS resin of one kind and preparation method thereof | |
| de Macedo et al. | Effect of processing conditions on the mechanical and morphological properties of elastomeric poly (methyl methacrylate)/polycarbonate blends | |
| CN109265972A (en) | The Matte thermoplastic polyurethane elastomer and preparation method thereof of easy processing high-modulus | |
| CN106009255A (en) | Antistatic modified polypropylene material and preparation method thereof | |
| CN110819017B (en) | Pellet and thermoplastic resin composition | |
| CN113444319A (en) | Antistatic polypropylene composite material and preparation method thereof | |
| TW201941222A (en) | Electrically conductive resin composition and method for producing same | |
| CN109747065A (en) | A kind of preparation method of phase shifter polyphenylene oxide resin based composites | |
| CN105647109A (en) | Polyether-ether-ketone/barium sulfate composite material, and preparation method thereof | |
| Moolsin | Cure characteristics, thermal and mechanical properties of natural rubber/synthetic rubber blends with and without compatibilizer | |
| CN110157134A (en) | A kind of modified styrene-butadiene-styrene block copolymer material and preparation method thereof | |
| CN109608869A (en) | Grease resistance high-impact PPO composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION, CHINA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZHANG, XIAOHONG;QIAO, JINLIANG;QI, GUICUN;AND OTHERS;REEL/FRAME:031685/0388 Effective date: 20130906 Owner name: BEIJING RESEARCH INSTITUTE OF CHEMICAL INDUSTRY, C Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZHANG, XIAOHONG;QIAO, JINLIANG;QI, GUICUN;AND OTHERS;REEL/FRAME:031685/0388 Effective date: 20130906 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |
|
| MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 8 |